n-Tetradecane is a typical heavy n-alkane component in transportation fuels. Nowadays, experimental data about n-tetradecane are rare, especially for the gas-phase kinetic experiment, which limits the development and updating of the combustion kinetic model of n-tetradecane. This paper reports the first effort on investigating the gas-phase pyrolysis of n-tetradecane. The experimental conditions cover temperatures of 832-1281 K and pressures of 30 and 760 Torr, while photoionization mass spectrometry was applied for speciation. A comprehensive model of n-tetradecane combustion was also constructed. The validation data include new pyrolysis data, literature oxidation data, and global combustion parameters. Modeling analysis tools were also applied to reveal major reactions for the pyrolysis and oxidation of n-tetradecane. Primary dissociation and H-abstraction reactions have the largest contributions and sensitivity coefficients for n-tetradecane decomposition under present pyrolysis conditions. HO2 plays a significant role on ignition delay times, while C-0-C-3 reactions dominate laminar burning velocities of n-tetradecane.